124 research outputs found
Instantaneous Pair Theory for High-Frequency Vibrational Energy Relaxation in Fluids
Notwithstanding the long and distinguished history of studies of vibrational
energy relaxation, exactly how it is that high frequency vibrations manage to
relax in a liquid remains somewhat of a mystery. Both experimental and
theoretical approaches seem to say that there is a natural frequency range
associated with intermolecular motions in liquids, typically spanning no more
than a few hundred cm^{-1}. Landau-Teller-like theories explain how a solvent
can absorb any vibrational energy within this "band", but how is it that
molecules can rid themselves of superfluous vibrational energies significantly
in excess of these values? We develop a theory for such processes based on the
idea that the crucial liquid motions are those that most rapidly modulate the
force on the vibrating coordinate -- and that by far the most important of
these motions are those involving what we have called the mutual nearest
neighbors of the vibrating solute. Specifically, we suggest that whenever there
is a single solvent molecule sufficiently close to the solute that the solvent
and solute are each other's nearest neighbors, then the instantaneous
scattering dynamics of the solute-solvent pair alone suffices to explain the
high frequency relaxation. The many-body features of the liquid only appear in
the guise of a purely equilibrium problem, that of finding the likelihood of
particularly effective solvent arrangements around the solute. These results
are tested numerically on model diatomic solutes dissolved in atomic fluids
(including the experimentally and theoretically interesting case of I_2 in Xe).
The instantaneous pair theory leads to results in quantitative agreement with
those obtained from far more laborious exact molecular dynamics simulations.Comment: 55 pages, 6 figures Scheduled to appear in J. Chem. Phys., Jan, 199
Ultrafast optical generation of coherent phonons in CdTe1-xSex quantum dots
We report on the impulsive generation of coherent optical phonons in
CdTe0.68Se0.32 nanocrystallites embedded in a glass matrix. Pump probe
experiments using femtosecond laser pulses were performed by tuning the laser
central energy to resonate with the absorption edge of the nanocrystals. We
identify two longitudinal optical phonons, one longitudinal acoustic phonon and
a fourth mode of a mixed longitudinal-transverse nature. The amplitude of the
optical phonons as a function of the laser central energy exhibits a resonance
that is well described by a model based on impulsive stimulated Raman
scattering. The phases of the coherent phonons reveal coupling between
different modes. At low power density excitations, the frequency of the optical
coherent phonons deviates from values obtained from spontaneous Raman
scattering. This behavior is ascribed to the presence of electronic impurity
states which modify the nanocrystal dielectric function and, thereby, the
frequency of the infrared-active phonons
Site-specific vibrational dynamics of the CD3 zeta membrane peptide using heterodyned two-dimensional infrared photon echo spectroscopy
Heterodyned two-dimensional infrared (2D IR) spectroscopy has been used to study the amide I vibrational dynamics of a 27-residue peptide in lipid vesicles that encompasses the transmembrane domain of the T-cell receptor CD3zeta. Using 1-C-13=O-18 isotope labeling, the amide I mode of the 49-Leucine residue was spectroscopically isolated and the homogeneous and inhomogeneous linewidths of this mode were measured by fitting the 2D IR spectrum collected with a photon echo pulse sequence. The pure dephasing and inhomogeneous linewidths are 2 and 32 cm(-1), respectively. The population relaxation time of the amide I band was measured with a transient grating, and it contributes 9 cm-1 to the linewidth. Comparison of the 49-Leucine amide I mode and the amide I band of the entire CD3zeta peptide reveals that the vibrational dynamics are not uniform along the length of the peptide. Possible origins for the large amount of inhomogeneity present at the 49-Leucine site are discussed. (C) 2004 American Institute of Physics
Speckle-free laser imaging
Many imaging applications require increasingly bright illumination sources,
motivating the replacement of conventional thermal light sources with light
emitting diodes (LEDs), superluminescent diodes (SLDs) and lasers. Despite
their brightness, lasers and SLDs are poorly suited for full-field imaging
applications because their high spatial coherence leads to coherent artifacts
known as speckle that corrupt image formation. We recently demonstrated that
random lasers can be engineered to provide low spatial coherence. Here, we
exploit the low spatial coherence of specifically-designed random lasers to
perform speckle-free full-field imaging in the setting of significant optical
scattering. We quantitatively demonstrate that images generated with random
laser illumination exhibit higher resolution than images generated with
spatially coherent illumination. By providing intense laser illumination
without the drawback of coherent artifacts, random lasers are well suited for a
host of full-field imaging applications from full-field microscopy to digital
light projector systems.Comment: 5 pages, 4 figure
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